JPH05302988A - Fuel cell type new energy generator - Google Patents

Abstract

PURPOSE:To realize an energy generator with good efficiency by supplying deuterium gas to a positive electrode and making a reaction expressed by a particular equation for changing the deuterium gas to deuterium ion. CONSTITUTION:In the case of using acid electrolyte 3 of D2SO4, deuterium gas D2 is introduced from outside through a valve 7 and the inner pressure of a sealed vessel 6 is set at a specified high pressure. Thus, solving velocity of gas D2 into the solution 3 is expedited and the soluble amount of balance of gas D2 in the solution 3 is increased. The gas D2 penetrates from the gas supply layer 15 in a gas diffusion electrode as a positive electrode 1, diffuses and reaches the boundary between the positive electrode 1 and the solution 3. At this boundary, a reaction occurs as follows. D2 2D<+>+2e<->. The produced ion D<+> reacts on the electron (e<->) supplied from an external power source 9 at a negative electrode 2 to be a deuterium atom D (a), which becomes gas D2 again and at the same time absorbed partly in the negative electrode 2. The electric potential impressed from outside to the positive electrode 1 is lower than 0.1V and the electric potential to cause reaction at the negative electrode 2 is about 0.3V and therefore, the input energy is low enough.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an energy generator capable of obtaining high output energy with respect to input energy.

[0002]

2. Description of the Related Art Energy generators were developed in March 1989.
Presented by Professor Ponce and Professor Fleischmann at the University of Utah in March. The equipment is lithium deuteride LiO.
Heavy water D ₂ O containing D is used as a cathode of a hydrogen storage metal material such as palladium, and platinum is used as an anode to supply a direct current to perform electrolysis. By continuously storing hydrogen atoms in the cathode, the device provided high output energy with respect to input energy.

[0003]

In a conventional energy generator using an alkaline electrolyte, a reaction for generating oxygen O ₂ as shown in formula (1) occurs at the anode.

[0004]

[Chemical 2]

Here, OD ^- and e ^- represent heavy hydroxide ions and electrons, respectively. In order for this reaction to occur, a potential of at least 1.7 V (RHE standard) is required, and since a large amount of energy is input to the energy generating device in this manner, it is a major factor that lowers the output / input energy ratio of the device. It was a cause. Further, since the electrolyte such as LiOD contained in the heavy water D ₂ O electrolytic solution has low electrical conductivity, Joule heat is generated due to the electrical resistance of the solution when electrolyzing, and the solution and the electrolytic cell are heated. .. Such heat generation is also one of the factors that lower the energy efficiency of this device by merely making the input energy extra heat energy.

Next, in an energy generator using an acidic electrolyte, conventionally, at the anode, heavy water molecules D ₂ O react to generate oxygen as shown by the following formula (7).

[0007]

[Chemical 3]

The oxygen O ₂ generation reaction in this acidic solution is more than the potential for carrying out the same reaction (Equation (1)) in the alkaline electrolyte, that is, the potential of at least about 1.7 V (RHE standard). It is known to require a high potential. Therefore, like the energy generating device using the alkaline electrolyte, it has been a main factor of reducing the output / input energy ratio of the device.

Further, conventionally, when the energy generating device is an open type, that is, when the electrolytic solution is alkaline or acidic, deuterium gas D ₂ generated at the cathode and oxygen gas O ₂ generated at the anode are out of the device. The heavy water D ₂ O is exhausted in the device for discharging to the device, so that the amount of liquid in the device is reduced, and it is necessary to replenish the heavy water D ₂ O at regular intervals.

Still further, a closed type energy generating device
Position, ie deuterium gas D₂And oxygen gas O₂The device again
Heavy water in₂In a device that converts to O, platinum or
The conversion device using a catalyst such as palladium and its temperature
Problems such as the need for a temperature controller to keep the temperature around 200 ° C
There was a point. Therefore, the present invention solves the above problems.
That is, energy efficient and heavy water D₂Elimination of O
Deuterium gas D with no wear ₂And oxygen gas O₂The heavy water D₂O
Energy generator that does not require a device to convert
The purpose is to provide.

[0011]

In order to solve the above problems, the present invention applies a voltage to an anode and a cathode consisting essentially of a hydrogen storage metal or its alloy in heavy water containing an electrolyte. In the method of performing the energy generation reaction by using the energy generation device of the type that performs the energy generation reaction by supplying the deuterium gas to the anode without causing the reaction of generating oxygen in the anode, formula

[0012]

[Chemical 4]

Deuterium gas D ₂ shown in [0013] deuterium ions D ⁺
And the reaction to be performed. Furthermore, the present invention is contacted with heavy water containing an electrolyte, a cathode consisting essentially of a hydrogen storage metal or an alloy thereof, and the energy generating device of the type to which a voltage is applied to the anode, deuterium D ₂ gas anode The energy generating device is characterized by having a means for introducing it into the energy generating device.

Furthermore, the present invention is an energy acquisition device in which energy extraction means is added to the energy generation device. To explain the means for solving the above problem in more detail, in the present invention, by supplying deuterium gas D ₂ to the anode, the following formula is obtained without causing a reaction to generate oxygen O ₂ at the anode.

[0015]

[Chemical 5]

Deuterium gas D ₂ shown in [0016] deuterium ions D ⁺
In order to carry out the reaction (1), any one of the following four means or a combination thereof is used. (1) The energy generator is of a sealed type, and the deuterium gas D ₂ is filled therein at a high pressure to increase the amount of the deuterium gas D ₂ dissolved in the electrolytic solution and to increase the gas phase deuterium gas D 2. ₂ increase the dissolution rate of the deuterium gas D ₂ into the liquid phase from.

(2) Deuterium gas D ₂ through the gas supply layer of the anode (gas diffusion electrode) consisting of the gas supply layer and the reaction layer
Is supplied to the reaction layer in contact with the electrolytic solution. (3) The anode is a gas permeable electrode made of palladium or palladium-silver alloy, and deuterium gas D ₂ is supplied into the anode in contact with the electrolytic solution through the anode surface not in contact with the electrolytic solution.

(4) Deuterium gas D ₂ is directly bubbled into the electrolytic solution and supplied. Further, the energy extraction means of the present invention is configured by thermally coupling the thermoelectric conversion element to the heat conducting / conducting member led from the cathode. In this specification, the terms “electrolysis” and “electrolyze” are used in the description of the present invention, but these terms are not used to mean that electrolysis of heavy water is performed. It means that a voltage in the range in which electrolysis of does not occur is applied to the electrodes.

[0019]

As described above, in the energy generator by the electrolysis method, the hydrogen storage metal such as palladium or its alloy must be used as the cathode, and the cathode must be filled with deuterium atoms D (a) at a high density. (1) LiO 2 LiO 3 as the electrolyte in the present invention
The reaction mechanism at the cathode of the energy generator using an alkaline heavy aqueous solution such as D is as follows.

[0020]

[Chemical 6]

The adsorbed deuterium atom D (a) generated on the cathode surface according to the formula (3) is absorbed into the cathode palladium as shown by the formula (5).
(Represented by (Pd)), or as shown by the formula (4), it becomes deuterium gas D ₂ and is released from the palladium surface. In order to carry out the reaction of formula (2),
A sufficient amount of deuterium gas D ₂ is supplied to the anode, and a voltage to be applied is much smaller than 1.7 V (RHE standard) which has been conventionally required. Since the reaction of the formula (2) is a fuel cell type reaction rather than an electrolysis type reaction, the voltage applied to the device for causing the reaction of the formula (2) to generate energy is usually about 0.3V
It is a degree.

More specifically, the applied voltage required for the reaction occurring at the anode, that is, the reaction represented by the formula (2) is about 0.1 V or less, and the reaction occurring at the cathode, that is, the formula Since the applied voltage required for the reactions shown in (3) and (4) is about 0.3V, the voltage applied to the entire energy generating device is normally about 0.4V as the sum. However, what should be taken into consideration at that time depends on the type of the electrolytic solution, but since the electrolytic solution has an electric resistance R, a voltage corresponding to the product iR of the electrolysis current i and the electric resistance R is increased and applied. There is a need to.

(2) In the present invention, D ₂ SO ₄ and DCl
When an acidic electrolytic solution such as the above is used, deuterium ions D ⁺ are discharged as in the following formula (6) instead of discharging heavy water molecules as in the formula (3) at the cathode.

[0024]

[Chemical 7]

Here, the adsorbed deuterium atom D generated on the cathode surface
As in the alkaline electrolyte, (a) is released as deuterium D ₂ gas as shown in formula (4), or diffuses and dissolves inside the cathode as shown in formula (5). .. As in the present invention, a gas diffusion electrode having a high activity for the ionization reaction of deuterium D ₂ gas is arranged as the anode represented by the formula (2), and the deuterium gas D ₂ is sufficiently supplied to the electrode. By ensuring that the electrolyte solution is alkaline or acidic, the reaction at the anode can be the reaction shown in formula (2), and the overvoltage required for charging the deuterium atom D (a) to the cathode can be significantly reduced. Therefore, the required input energy to the energy generator can be reduced.

Here, from the viewpoint of the reaction of the entire device by summing up the individual reactions at the anode and the cathode, in the conventional energy generator, if the electrolyte is alkaline, the formulas (3), (4), As the sum of the formulas (5) and (1), the sum of the formulas (6) and (7) in the case of acid is

[0027]

[Chemical 8]

As shown by, heavy water D ₂ O is electrolyzed to generate deuterium gas D ₂ and oxygen gas O ₂ , and deuterium D 2
Part of is dissolved and absorbed inside the palladium. At this time, since the deuterium atoms D (a) filled in the cathode are supplied from the heavy water molecule D ₂ O, the heavy water D ₂ O is consumed in the conventional energy generator. However, in the energy generator of the present invention, in the alkaline electrolyte, the cathodic reaction is given by the equations (3), (4) and (5) as in the conventional type, but the anodic reaction is given by the equation (2). Therefore, deuterium ions D ⁺ generated at the anode and heavy hydroxide ions OD ⁻ generated at the cathode react with each other to return to heavy water D ₂ O, so that it is not exhaustion due to electrolysis of heavy water D ₂ O that occurs as a whole. Only the deuterium gas D ₂ is consumed by the dissolution and absorption of the deuterium gas D _{2 in} the cathode. On the other hand, also in the acidic electrolyte, the deuterium ion D ⁺ generated by the anodic reaction of the deuterium gas D _{2 represented by} the formula (2) is discharged at the cathode as shown in the formula (6) and the deuterium atom is again generated. Since it returns to D (a), the consumption of heavy water D ₂ O or the electrolyte does not occur as a whole, and only the pressure drop of the heavy water D ₂ O due to the dissolution and absorption of the heavy hydrogen gas D _{2 in} the cathode occurs. Occur.

It is known that hydrogen-storing metals and alloys such as palladium can absorb deuterium gas D ₂ having a volume of 900 to 1000 times the volume in general, and in consideration of this point, in advance. The initial deuterium pressure of the energy generator of the present invention is set so that the gas pressure of the final deuterium gas D ₂ after filling the cathode with deuterium D is not more than a pressure sufficient to prevent boiling due to the temperature rise of the electrolyte. If this is not done, this initial pressure will only decrease during the operation of the device, and there is no need to supplement the deuterium gas D ₂ .

On the other hand, in the energy generator of the present invention in which the reaction at the anode is not the generation of oxygen gas O ₂ but the ionization reaction of deuterium gas D ₂ , the filling of deuterium D ₂ into the cathode is effective. In achieving this, it has the following advantages. The deuterium atoms D (a) generated and adsorbed on the cathode are liberated as deuterium gas D ₂ as shown in formula (4), or deuterium atoms as shown in formula (5). D
As in (a), the formula (4) is used to determine whether diffusion and dissolution will occur inside the cathode.
It is determined by the relative relationship between the reaction rate of Eq. (5) and the rate of the diffusion and dissolution process of deuterium D inside the cathode of the formula (5). In order to effectively fill the cathode with deuterium D, it is desirable that the reaction of formula (4) is slow. It is known that a surface-active substance such as thiourea may be added to the electrolytic solution in order to delay the reaction of the formula (4). However, in the conventional energy generator, the potential of the anode is oxygen gas O ₂ Since it is at the generated potential (1.7 V or more based on RHE), it is oxidized and decomposed at the anode even if these surface-active substances are added.

However, in the energy generator of the present invention, since the potential of the anode is at the ionization potential of D ₂ gas (0.1 V or less based on RHE), the above-mentioned surface-active substances are not oxidized or decomposed at the anode. Therefore, when the operation of the energy generation device of the present invention is performed in the coexistence of the surface-active substance, deuterium D can be more effectively charged into the cathode with respect to a constant input power, and the device can be further improved. The efficiency of can be realized.

[0032]

[Embodiment 1] FIG. 1 shows an embodiment of a closed type energy generating apparatus of the present invention. The anode 1 has a tubular shape, and the anode 1
The bottom 14 is adhered to the lower part of the container to form a container as a whole. The entire container-shaped anode is fixedly installed in the closed container 6 so as to separate a space. At least a part or all of the tubular side wall of the tubular anode 1 carries a reaction layer 5 carrying a catalytic metal having a high activity for ionizing deuterium gas such as platinum or palladium, and a water-repellent gas bonded thereto. The gas diffusion electrode is composed of the supply layer 15. When a part of the side wall is a gas diffusion electrode, the reaction layer 5 has a thickness of 0.1 to 0.2 mm,
One side of the reaction layer 5 has a porosity and water repellency of 0.5 to 0.8.
A mm gas diffusive gas supply layer 15 is bonded and attached so as to be the outer surface of the side wall. Gas supply layer 15
A current collecting net 11 made of a conductive material for collecting current
Is embedded, and the current collecting network 11 is connected to the terminal 10 for inputting an external voltage into the energy generating device. The reaction layer 5 is composed of platinum powder or palladium powder, hydrophilic carbon powder, 10 wt% of polytetrafluoroethylene (PTFE), and platinum or palladium powder is uniformly supported on the reaction layer. As a result, it is hydrophilic and easily reacts with the electrolytic solution.

As a method for supporting platinum on the reaction layer 5, a coating method and a colloid method can be used. (A) In the coating method, after the reaction layer 5 not yet supporting platinum and the gas supply layer 15 are press-molded, a platinum solution, that is, usually chloroplatinic acid H ₂ PtCl ₆ is applied to the reaction layer 5 of the molded product.
It is prepared by coating and impregnating a solution and then reducing it with hydrogen gas in an electric furnace.

(B) The colloid method is chloroplatinic acid H ₂ Pt.
Hydrophilic carbon powder, which is a raw material for the reaction layer, is directly added to a platinum colloidal solution obtained by reducing the Cl ₆ solution with a reducing agent,
A platinum colloid is supported on the powder, filtered, reduced with hydrogen gas in an electric furnace to obtain platinum-supporting carbon powder, and this powder is press-molded. In each of the reaction layers 5 obtained by the coating method and the colloid method, the amount of platinum supported is usually about 0.5 to 1.0 mg / cm ² .

A material having a hydrogen / corrosion resistance is used as a material that is bonded to the bottom of the anode 1 to form the bottom 14, and preferably stainless steel, Hastelloy (trade name), and Inconel (trade name) are used. .. The inside of the bottomed cylindrical portion including the anode 1 has a structure capable of holding the electrolytic solution 3. At the center line position of the inner space of the bottomed cylindrical portion, a cathode 2 of a hydrogen storage metal such as rod-shaped palladium or an alloy thereof having a heat conducting / conductive member 4 made of silver Ag, copper Cu or the like as a core is inserted. It is fixed to the hermetically sealed container 6 by a heat-resistant, hydrogen-resistant, and corrosion-resistant insulating seal member 13 (sealing grant, product name) so as to maintain a hermetically sealed state. The member 4 is connected to the external power supply 9. The heat conducting / conducting member 4 is extended to the outside of the closed container 6 and has a function of taking out the thermal energy generated in the palladium member 2 of the cathode 2 to the outside of the closed container 6.

Deuterium gas D ₂ is introduced into the closed container 6 through the valve 7, and the closed container 6 is filled with the deuterium gas D ₂ . The material of the closed container 6 is made of a material having hydrogen resistance and corrosion resistance, and specifically, stainless steel, Hastelloy (trade name), Inconel (trade name), SUS316 (trade name), plastic such as fluororesin, Glass can be used.

The terminal 10 is an insulating seal member 12 having hydrogen resistance and corrosion resistance, such as a sealing grant (trade name).
Is fixed to the hermetically sealed container 6 so as to maintain a hermetically sealed state, and the terminal 10 is connected to an external power source 9. The external power source 9 is adapted to apply a voltage between the anode 1 and the cathode 2. Anode 1 and bottom 14
The container-like object formed from is fixed on an insulating pedestal 16 installed at the bottom of the closed container 6. Also, the cylindrical anode 1
In order to reinforce the strength of (1), a frame-shaped, insulative support member that does not prevent the supply of deuterium gas D _{2 to} the anode 1 from the outside may be attached.

An electrolytic solution 3 is filled in the bottomed cylindrical portion in such an energy generator, and the electrolytic solution 3 contains deuterated lithium hydroxide as an alkaline electrolyte in heavy water D ₂ O. A solution of LiOD, bisulfate D ₂ SO ₄ or deuterium chloride DCl is used. Further, a surface-active substance such as thiourea may be added to the electrolytic solution 3 in order to suppress the reaction represented by the formula (4).

Next, the operation of this energy generator will be described with reference to the conceptual diagram of FIG. This FIG. 2 shows an energy generator in the case of an acidic electrolyte using D ₂ SO ₄ , DCl, etc. as the electrolyte. The device itself is the same as in FIG. Deuterium gas D from outside through valve 7
₂ is introduced to adjust the internal pressure of the closed container 6 to 10 kg / cm ²
High pressure up to the front and back. Under such a pressure, the dissolution rate from the vapor-phase deuterium gas D ₂ to the liquid-phase electrolyte solution 3 is increased, and the equilibrium dissolution amount of the deuterium gas D ₂ in the electrolyte solution 3 is increased. The path for the deuterium gas D ₂ to reach the anode 1 is
The gas supply layer 15 of the gas diffusion electrode, which is the anode 1 mainly surrounded by the deuterium gas D ₂ rather than from the electrolytic solution 3.
Deuterium gas D ₂ permeates and diffuses from the anode 1 and the electrolyte 3
Reach the interface.

At this interface, the reaction of the above formula (2) occurs.
Conventionally, heavy water has to be electrolyzed to generate energy, and the voltage required to cause the electrolysis is 1.7 V, which is the minimum required for oxygen generation on the anode 1 side.
A minimum of about 2V, which is the sum of (RHE standard) and about 0.3V (RHE standard) required for deuterium gas generation at the cathode 2, was required. In the present invention, deuterium gas D ₂ is positively supplied to the anode 1 which is a gas diffusion electrode, so that the deuterium gas D ₂ is ionized at the anode 1 and the generated deuterium ion D ⁺ is expressed by the formula ( As shown in 6), the cathode 2 reacts with the electron e ⁻ supplied from the external power source 9 to form the deuterium atom D (a), and again the deuterium gas D _{2 as} shown in the formulas (4) and (5). At the same time, a part is occluded in the cathode 2.

When an alkaline heavy aqueous solution such as LiOD is used as the electrolytic solution 3, deuterium ions D ⁺ generated by the reaction of the formula (2) at the anode 1 are generated at the cathode 2 by the reaction of the formula (3). heavy hydroxide ions OD was ^- reacted so return to heavy water D ₂ O in the heavy water D ₂ O consumption canceled out by anode 1 at the cathode 2, the consumption of heavy water D ₂ O as a result of the reaction of the whole cathode 2 Does not happen.

The ionization reaction of the deuterium gas D _{2 represented by} the formula (2) is carried out by the anode 1 carrying a catalyst such as platinum or palladium.
The potential applied from the outside to cause the above is 0.1 V or less (RHE standard), and the potential for causing the reactions of the formulas (4) and (5) at the cathode 2 is about 0.3 V ( Since it is RHE standard), the cell voltage is about 0.4V. Therefore, the energy generation reaction can be performed with a voltage much lower than the minimum cell voltage of about 2 V when the conventional reaction of the above formula (1) occurs at the anode 1, that is, with less input energy.

By monitoring the deuterium pressure in the container after the start of electrolysis, the filling process of deuterium into the cathode and the filling rate (D / P _d atomic ratio) can be known with respect to the electrolysis time. You can gain valuable information to control energy generation. Furthermore, in this embodiment, the cathode 2
The heat conducting / conductive member 4 is used therein, but this is for taking out excess heat generated by energy generation to the outside of the energy generating device by the heat conducting / conductive member 4 for use.

Furthermore, when the excess heat is used for heating the electrolytic solution 3 and the thermal energy of the obtained high temperature electrolytic solution is used, it is not necessary to use the heat conducting / conducting member 4 and a current is simply passed. It is only necessary to connect the lead wire for Next, as an anode configuration, an example of an anode made of a flat panel will be shown. This embodiment will be described with reference to FIG. The so-called gas diffusion electrode that constitutes the anode is usually a press-formed porous reaction layer and gas supply layer, and is a flat anode panel made by press-forming due to the ease of molding technology. At 21, an anode of this example was prepared. A cylindrical wall is formed by four anode panels 21, and is fixed by a supporting member 22 around the upper end and the lower end thereof, and
The supporting member 23 was fixed to the joining portion of the four panels, that is, the four ridge portions of the rectangular parallelepiped to form a quadrangular prism. A bottom member was bonded to the lower portion of this square column by adhesion to form a square columnar container. The anode composed of this square column-shaped container can be used instead of the anode of FIG. The four anode panels are wired so that currents are respectively supplied from an external power supply.

Next, an embodiment of an energy acquisition device in which energy extraction means is added to the energy generation device of the present invention will be described. FIG. 4 shows the energy acquisition device of this embodiment. In this embodiment, the heat conducting / conducting member 4 of the energy generating apparatus shown in FIG.
A thermoelectric conversion device 18 is attached to the extension of the conductive member 4 as an energy extracting means. The heat insulating material 17 coated on the thermoelectric / conductive member 4 is for cutting off heat so that the heat energy generated in the cathode 2 is not lost to the thermoelectric conversion element 18 as much as possible. The thermoelectric conversion element 18 is thermally coupled and attached to the extension portion of the heat conducting / conductive member 4 extending to the outside of the closed container 6. The thermoelectric conversion element 18 is an element that converts the heat energy generated by the energy generating device into electric energy, and is a means for making the heat generated from this device usable as electric energy.

Further, in FIG. 5, the wiring on the negative side of the external voltage applied to the energy acquisition device shown in FIG.
An example in which the palladium member 8 of the cathode 2 is directly connected without being connected to the conductive member 4 is shown.

[0047]

Example 2 The anode used in Example 1 was a gas diffusion electrode having a gas supply layer and a reaction layer for carrying out the deuterium ionization reaction. Instead of the anode of No. 1, an energy generator using an electrode made of a hydrogen storage metal such as palladium or a palladium-silver alloy was used.

FIG. 6 shows the energy generator of this embodiment. The configuration other than the anode 31 is the same as that of FIG. 4 described in the first embodiment. The deuterium gas permeation capacity of an electrode made of a hydrogen storage metal such as palladium or a palladium-silver alloy is slightly inferior to that of a gas diffusion electrode, but the activity for deuterium gas ionization reaction does not change, so electrolysis When the current is below a certain level, the energy generator of this embodiment can sufficiently cope with the situation.

Various anode structures are conceivable in this embodiment. When palladium or a palladium-silver alloy is directly formed into a cylinder, the bottom 31 at one end of the cylinder is used.
A disc or a square plate made of the same metal as the metal of the cylinder or a corrosion-resistant insulating material is welded or bonded to the portion to be the bottom 31
4 is formed. When the sheet or film of palladium or palladium-silver alloy is used as the anode, a window is opened in the side surface of the bottomed insulating container made of a corrosion-resistant insulating material, and the anode sheet or the anode film is placed in this empty portion. As an electrode, they are joined by adhesion to form a container-shaped anode. Furthermore, as shown in FIGS. 7 and 8, instead of the insulating container,
A window 325 is formed in the center, and a flat plate-shaped insulating panel 333 in which the above-mentioned anode sheet or anode film 324 is used as an electrode and bonded by adhesion to the open portion is formed by the rectangular columnar container described in Embodiment 1 with reference to FIG. It is made in the same way as the anode. FIG. 7 shows the flat insulating panel, and FIG.
Shows an energy acquisition device made by using an anode composed of the flat insulating panel.

[0050]

[Embodiment 3] FIG. 9 shows an embodiment of the open type energy generating apparatus of the present invention. This device is a device in which a deuterium gas blowing device is added to a commonly used heavy water electrolysis type energy generator. The configuration of this device will be described with reference to FIG. The electrolytic solution 43 is filled in the container 44 which is partially opened to the external space through the upper opening tube 46.
In the electrolytic solution 44, a cathode 42 made of a hydrogen storage type metal such as palladium and an alloy and an anode 41 made of platinum or the like are arranged at a distance from the cathode 42. Container 44
A deuterium gas blowing device 45 for blowing and introducing deuterium gas D ₂ into the electrolytic solution is arranged therein.

Further, in order to reinforce the strength of the anode 41 as a whole, an insulating support member 48 partially reinforces a required portion of the anode 41. Furthermore, the support member 48 supporting the anode is supported and fixed to the container 44 containing the electrolytic solution 43 by an insulating support piece 47. Anode 4
1 and cathode 42 are each connected through terminals 48 to an external power supply 49 external to the container.

When the energy generator is operated, the deuterium gas D ₂ introduced from the outside by the deuterium gas blowing device 45 is blown into the electrolytic solution 43. The injected deuterium gas D ₂ is dissolved in the electrolytic solution and diffuses at the interface of the anode 41, and the reaction of the above formula (2) occurs at this interface. In addition, the electrolytic solution 4 generated by blowing the deuterium gas D ₂
Due to the convection of 3, the deuterium gas D ₂ is uniformly dissolved in the electrolytic solution and supplied to the anode.

[0053]

Fourth Embodiment FIG. 10 shows still another embodiment of the energy generator of the present invention. This is obtained by removing the deuterium gas blowing device from the open type device shown in FIG.
6 has a valve 55. Such a device is filled with deuterium gas at a high pressure, the electrolyte solution 53 (electrolyte + heavy water) is saturated with deuterium gas, and a cathode 52 made of a hydrogen storage metal such as palladium or an alloy thereof is formed at a constant current or a constant potential. A voltage is applied to the anode 51 to cause the reactions represented by the formulas (2), (3), (4) and (5) to generate energy. At this time, deuterium gas molecule D ₂
Is diffused in the electrolytic solution and supplied to the anode 51, and is ionized as shown in the reaction formula (2).

If the saturated deuterium gas concentration in the electrolyte solution 53 is sufficiently high, the limiting diffusion current of the ionization reaction of the deuterium gas D ₂ at the anode 51 represented by the formula (2) is the deuterium D to the cathode 52. Since the reaction of equation (2) can cover the electrolysis current if it is larger than the electrolysis current for filling
The reaction occurring at the anode is exclusively the reaction represented by the formula (2), and the reaction at the anode 51 is represented by the formula (1) (in the case of alkaline electrolyte).
Alternatively, oxygen O ₂ according to formula (7) (in the case of acidic electrolyte)
Does not occur. As a result, an energy generator with high energy efficiency can be realized as in the other embodiments.

However, if the deuterium D ₂ gas pressure in the apparatus is not sufficiently high, the concentration of deuterium in the electrolytic solution will not rise and the reaction of the formula (2) at the anode cannot bear the entire electrolytic current. The occurrence of ₂ also occurs. The deuterium gas pressure P in the apparatus and the deuterium gas saturation concentration C to the electrolytic solution are almost in a proportional relationship, and the limiting diffusion current i _L of the deuterium gas ionization reaction by the reaction of the formula (2) is in the electrolytic solution. Therefore, the limit diffusion current i _L is almost proportional to the deuterium gas pressure P.

It is known that the deuterium gas saturation concentration C when the deuterium gas pressure P is 1 atm is about 1 mM / l at room temperature, and the limiting diffusion current i _{L at} this time is usually ² to 3 mA / cm ^2. Has been. Therefore, according to the present embodiment, in order to generate energy and make the reaction at the anode 51 only the reaction represented by the formula (2), the electrolytic current density is the limiting diffusion current i.
_The deuterium gas pressure P must be adjusted so that it does not exceed _L. If the deuterium gas D ₂ sufficient to absorb deuterium atoms D (a) into the cathode 52 at a high filling rate cannot be enclosed in the container 54 due to the small empty volume in the container 54, the container 54 and a valve It is advisable to provide a reservoir tank having an appropriate volume with 55.

In this embodiment, the electrolytic solution was heavy water D ₂ O containing deuterated lithium hydroxide LiOD, but instead of LiOD, it is possible to use deuterated hydrochloric acid DCl or bisulfuric acid D ₂ SO ₄ . Particularly, since the aqueous solution of deuterated hydrochloric acid DCL or the aqueous solution of bisulfuric acid D ₂ SO ₄ is excellent in electric conductivity, Joule heat is less generated during electrolysis, and the energy efficiency is better than that of lithium hydroxide LiOD.

[0058]

[Embodiment 5] This embodiment shows still another embodiment of the closed type energy generating device. This device was designed specifically to identify energy production. Alkaline
Energy generation device using deconstruction Fig. 11 and Fig. 12
Shows a sectional view of an energy generator using an alkaline electrolyte, that is, lithium hydroxide LiOD and heavy water D ₂ O as the electrolyte. 11 and 12 show different cross sections of the same device, respectively.

Reference numeral 100 denotes an electrolytic cell, and the electrolytic cell 100 is roughly divided into three parts, namely, an electrolytic cell lower part, an electrolytic cell middle part, and an electrolytic cell upper part. The lower part of the electrolytic cell is the lower part of the electrolytic cell 100. The lower part of the electrolyzer is composed of a bottom plate 104 at the bottom of the electrolyzer 100, and a fixer 105 made of Teflon (registered trademark) that is in contact with the bottom plate 104 and fixedly supports the cathode 102 made of palladium. It is mainly composed.

The middle part of the electrolytic cell is an important part for carrying out the energy generation reaction, and the anode 101 composed of a tubular gas diffusion electrode, and the anode 101 at the substantial center of the tubular anode 101.
Is mainly composed of a cathode 102 which is located with a space therebetween. The upper part of the electrolytic cell has an electrolytic solution container 107 made of a cylindrical quartz glass tube. The lower portion of the electrolytic solution container 107 has a taper that narrows downward, and the lower portion is joined to the cylindrical anode 101 described above. A stopper 108 made of Teflon (registered trademark) is provided on the upper portion of the electrolytic solution container 107.

In the electrolytic cell 100 having the above-mentioned structure,
The electrolytic solution 103 is filled up to the upper side of the electrolytic solution container 107. Lead wires are connected to the anode 101 and the cathode 102, respectively, and are connected to an external power source. Further, the reference electrode 109 is immersed in the electrolytic solution 103 and taken out to the outside. Further, thermocouples 110 for monitoring the internal temperature are provided in the central portion of the cathode 102 and the electrolytic solution 103, respectively. Furthermore, the electrolytic solution 103
A heater 113 made of a nichrome wire for heating the electrolytic solution 103 is provided therein.

The entire electrolytic cell 100 is arranged in the pressure vessel 106, and the pressure vessel lid 112 is provided above the pressure vessel 106.
Is sealed by. Further, the electrolytic cell 100 is supported by an electrolytic cell holder 111 fixed to a pressure vessel lid 112. High-pressure deuterium gas 115 is introduced into the pressure vessel 106 from the outside through the gas pipe 114 and filled in the electrolytic solution 103.

Energy Generator Using Acid Electrolyte FIGS. 13 and 14 are sectional views of an energy generator using an acid electrolyte, that is, sulfuric acid D ₂ SO ₄ and heavy water D ₂ O as electrolytes. 13 and 14 show different cross sections of the same device, respectively. Reference numeral 200 denotes an electrolytic cell, and the electrolytic cell 200 is roughly divided into three parts, namely, an electrolytic cell lower part, an electrolytic cell middle part, and an electrolytic cell upper part.

The lower part of the electrolytic cell is the lower part of the electrolytic cell 200. The lower part of the electrolyzer is composed of a bottom plate 204 at the bottom of the electrolyzer 200, and a fixer 205 made of Teflon (registered trademark) that is in contact with the bottom plate 204 and fixes and supports the cathode 202 made of palladium. It is mainly composed. The middle part of the electrolytic cell is an important part for carrying out energy generating reaction, and is an anode 201 composed of a tubular gas diffusion electrode.
In addition, the cathode 202 is mainly composed of a cathode 202 which is located substantially at the center of the cylindrical anode 201 with a space from the anode 201.

The upper part of the electrolytic cell has an electrolytic solution container 207 made of a tube made of quartz glass or Pyrex (registered trademark) having a taper that spreads upward, and the lower part of the electrolytic solution container 207 is It is joined to the cylindrical anode 201 described above. A stopper 208 made of Teflon (registered trademark) is provided on the upper portion of the electrolytic solution container 207. The electrolytic cell 200 configured as described above includes the electrolytic solution container 2
The electrolyte 203 is filled up to above 07. Anode 2
Lead wires are connected to 01 and the cathode 202, respectively, and are connected to an external power supply. Further, the reference electrode 209 is immersed in the electrolytic solution 203 and taken out to the outside. In addition, a thermocouple 2 for monitoring the internal temperature
10 are provided in the central portion of the cathode 202 and in the electrolytic solution 203, respectively. Furthermore, a heater 2 made of a nichrome wire for heating the electrolytic solution 203 is provided in the electrolytic solution 203.
13 are provided.

The entire electrolytic cell 200 is placed in a pressure vessel 206, and a pressure vessel lid 212 is provided above the pressure vessel 206.
Is sealed by. The electrolytic cell 200 is supported by an electrolytic cell holder 211 fixed to the pressure vessel lid 212. High-pressure deuterium gas 215 is introduced into the pressure vessel 206 from the outside through the gas pipe 214 into the electrolytic solution 203 to be filled therein.

The effectiveness of the energy generator of the present invention will be shown below based on experimental data using the energy generator having the above-mentioned alkaline electrolyte and the energy generator having the acid electrolyte of the present embodiment. Experiment of Energy Generator Using Acid Electrolyte First, in order to prove that deuterium D is absorbed by the palladium cathode 202 of the energy generator using sulfuric acid D ₂ SO ₄ and heavy water D ₂ O as the electrolytic solution. Then, an experiment was conducted by immersing the entire energy generating device in a constant temperature water tank at 30 ° C. The electrolyte was set to 2.8 MD ₂ SO ₄ , the externally applied current density was set to 0.1 A / cm ² , the applied voltage was set to 0.7 V, and the input power was set to 0.3 W to operate the energy generation device.

The results are shown in the graph of FIG. Figure 15
Is the number of days of electrolysis on the horizontal axis and the temperature of the electrodes and the electrolytic solution and the gas pressure of deuterium gas on the vertical axis. The temperature of the palladium cathode was measured by a thermocouple 210 provided in the cathode 202, and the temperature of the electrolytic solution 203 was measured by a thermocouple 210 provided in the electrolytic solution 203. The curve A is the change in gas pressure of the deuterium gas D ₂ filled in the energy generator. The gas pressure, which was initially about 5.5 Kg / cm ² , suddenly dropped at the beginning of the operation, and then gradually decreased after 2 days of operation, and finally 4.15 Kg / cm ^2.
You can see that it has fallen to the extent. The curve of B is the cathode 202
It shows the temperature of the cathode measured by the thermocouple 210 provided inside. Further, the curve C shows the temperature of the electrolytic solution 203 measured by the thermocouple 210 provided in the electrolytic solution 203. Both temperature curves show the well-known peculiar exothermic reaction observed when deuterium D was occluded in palladium at the beginning of operation. After that, the temperature was gradually maintained at a substantially constant temperature due to thermal equilibrium between the Joule heat mainly generated in the electrolytic solution and the heat in the constant temperature bath outside the energy generator.

According to this experiment, the present energy generator monitored that deuterium D was effectively occluded in the palladium cathode 202. The palladium cathode 2
The mechanism by which the deuterium D is occluded in 02 is as described in Example 1 with reference to FIG. Next, an energy generation device using sulfuric acid D ₂ SO ₄ and heavy water D ₂ O in the electrolytic solution of the present invention was operated, and an experiment for confirming generation of excess heat was conducted as follows. Electrolyte 2.8M
D ₂ SO ₄ and the externally applied current density is 0.1 A /
cm ^2, and the applied voltage 0.7 V, the input power was operated energy generating device with 0.3 W. Also,
The electrolytic solution was 2.8 MD ₂ SO ₄ , the externally applied current density was 0.3 A / cm ² , the applied voltage was 1.2 V, and the energy generator was operated at an input power of 1.7 W. From external power source to cathode 202 and anode 201
Temperature rise of the cathode 202 with respect to the electrolysis power applied to
T (Pd) was measured.

The results are shown in the graph of FIG. The white circles in the graph indicate the temperature rise when operating at a current density of 0.1 A / cm ² . The black triangles in the graph show the temperature rise when operating at a current density of 0.3 A / cm ² . In order to compare how much excess heat is generated, a heater calibration value obtained by measuring how the temperature of the cathode rises according to the electric power supplied to the heater 213 provided around the cathode 202 is set to x. It is plotted with a mark.
This plot became a straight line.

With respect to this straight line, the current density is 0.1 A / c
It can be seen that the temperature rise when operated at m ² and 0.3 A / cm ² is larger than that when the same electric power is applied to the heater 213 as compared to the heater calibration in any operation. It can be seen from the 16 graphs. This indicates that the energy generator of the present invention was operated and excessive heat was generated.

Next, as a comparative experiment of the above experiment, sulfuric acid H was added to the electrolytic solution in order to use light hydrogen instead of deuterium.
₂ SO ₄ and water H ₂ O were used, but the current density was 0.1 A / cm ² and 0.3 A / cm ² using the same device as in the above experiment.
An experiment was conducted as to whether excessive heat generation occurred at ² , 0.49 A / cm ² . FIG. 17 is a graph showing the results of the experiment. White circles in FIG. 17 are values obtained by calibration by the heater. Black circles indicate current density of 0.1A
5 is a plot of input power and temperature rise given as / cm ² , 0.3 A / cm ² , 0.49 A / cm ² .

Both plots are on a straight line, which shows that the same result is obtained regardless of whether electric power is applied to the heater or electrolysis current, and that excessive heat is not generated. There is. Experiment of Energy Generation Device Using Alkaline Electrolyte FIG. 18 is a graph showing the results of temperature rise when power is applied to the energy generation device using lithium hydroxide LiOD and heavy water D ₂ O as the electrolytic solution. ..

In the experiment, the temperature rise of the cathode during electrolysis in 0.5 M LiOD and the calibration when the electrolytic solution was heated by the heater 113 were compared. The portion indicated by the solid line is a straight line created by plotting the temperature rise of the electrolytic solution when power is applied by the heater 113. The temperature rise was plotted based on the actual applied power for comparison with this straight line. Black circles show the temperature rise value of the electrolytic solution, and white circles show the temperature rise value of the palladium cathode with respect to the input power when an electrolytic current is passed. Immediately after increasing the electrolysis current density to 0.2 A / cm ² , the difference between the cathode temperature and the calibration was about 1.8 ° C. this is,
About 12.5% excess heat (0.51W for about 1.6W input)
/ Cm ² ).

Although the power applied to the electrodes is the same as the power applied to the heater 113, the temperature rise of the palladium cathode is large in any operation as compared with the heater calibration, as shown in the graph of FIG. As shown, this indicates that the energy generating device of the present invention was operated and excess heat was generated. Energy Generator of the Invention and PCT Application WO 90/1
Comparison of operating data with 0935 Let us compare the operating data of the energy generator of the present invention with the energy generator described in PCT application WO 90/10935 invented by Ponce / Fleishman et al.

Table 1 shows the operation data of the energy generator of the present invention. The cathode used was made of palladium and had a diameter of 5 mm and a length of 30 mm.

[0077]

[Table 1]

Table 2 shows PCT application WO 90/10935.
From the data published on page 68 of the above, data showing the portion most approximate to the current density of the electrolytic current used in the present invention is shown. The cathode is made of palladium and has a diameter of 1 mm and a length of 10 c.
m was used.

[0079]

[Table 2]

In the device of the present invention, the current density is 0.1 A / cm.
^The input power, that is, the power consumption was 0.57 W when operated with 0.5 M LiOD as the electrolyte in step ² , whereas the PCT application had an approximate current density of 0.17 W.
The power consumption when operating with 0.1 M LiOD as the electrolyte at 28 A / cm ² is 1.61 W, and it can be seen that the energy generation device of the present invention can be operated with a power consumption that is less than about one third.

In the device of the present invention, the current density is 0.3 A /
If the 2.8MD ₂ SO ₄ A electrolyte solution cm ^2, and optionally also the 0.5MLiOD at a current density 0.2 A / cm ² was operated as an electrolytic solution is more energy generator of the present invention of the the Similarly, it can be seen that, on average, the operation can be performed with a low power consumption of about 1/3 to 1/4. Example 1 above
5 to 5, the energy generator is mainly described, but it is obvious that the energy generator of the present invention can be used as a neutron generator and also as a tritium generator.

[0082]

As described above in detail, according to the energy generating apparatus of the present invention, oxygen O ₂ is generated at the anode as shown in the above formula (1), but the above formula (2) is generated.
Ionization of deuterium gas D ₂ represented by Therefore, the reaction at the anode represented by the above formula (1) is performed with oxygen O ₂
In the energy generating device of the present invention, the voltage applied from the outside may be much lower than that in the case of using the conventional energy generating device for the generation reaction of, so that the input energy required for generating the energy is small. It is possible to obtain an energy generating device with high energy efficiency. Also, since heavy water is not consumed by electrolysis unlike the conventional device, output energy can be obtained for a long time by supplying deuterium gas to the anode without supplying heavy water.

By introducing a surface-active substance such as thiourea into the electrolytic solution, the efficiency of filling deuterium in the cathode can be further improved.

[Brief description of drawings]

FIG. 1 shows a closed energy generator.

FIG. 2 is a conceptual diagram in which deuterium gas is ionized at the anode and becomes D ⁺ , which is stored as D as a result of the electrode reaction in the hydrogen storage metal of the cathode.

FIG. 3 shows an anode of a quadrangular prismatic container using an anode panel.

FIG. 4 shows an energy acquisition device according to an embodiment of the present invention.

FIG. 5 shows an energy acquisition device according to another embodiment of the present invention.

FIG. 6 shows an energy generator using palladium or its alloy as an anode.

FIG. 7 shows a sheet or film of palladium or its alloy as an anode.

FIG. 8 shows an energy generator using a sheet or film of palladium or its alloy as an anode.

FIG. 9 shows an open energy generator.

FIG. 10 shows a sealed energy generator filled with high-pressure deuterium gas.

FIG. 11 is a sectional view of an energy generator using lithium hydroxide LiOD and heavy water D ₂ O as an electrolytic solution.

FIG. 12 is another cross-sectional view of the energy generator using lithium hydroxide LiOD and heavy water D ₂ O as the electrolytic solution.

FIG. 13 is a cross-sectional view of an energy generator using sulfuric acid D ₂ SO ₄ and heavy water D ₂ O as electrolytic solutions.

FIG. 14 is another cross-sectional view of the energy generator using sulfuric acid D ₂ SO ₄ and heavy water D ₂ O as the electrolytic solution.

FIG. 15: Palladium cathode 202 of the energy generator of the present invention using sulfuric acid D ₂ SO ₄ and heavy water D ₂ O as the electrolytic solution
3 is a graph showing that deuterium D is absorbed by the.

FIG. 16 is a graph showing generation of excess heat when the energy generator of the present invention is operated using sulfuric acid D ₂ SO ₄ and heavy water D ₂ O as the electrolytic solution.

FIG. 17 is a graph for comparison with FIG. 16 in which the energy generating apparatus of the present invention is operated using sulfuric acid H ₂ SO ₄ and heavy water H ₂ O as the electrolytic solution.

FIG. 18 is a graph showing generation of excess heat when power is applied to the energy generator of the present invention using lithium hydroxide LiOD and heavy water D ₂ O as an electrolytic solution.

[Explanation of symbols]

1, 31, 41, 51, 101, 201 Anode 2, 32, 42, 52, 102, 202 Cathode 14, 314 Bottom 4, 34 Heat conduction / conductive member 7, 37, 55 Valve 3, 33, 43, 53, 103,203 Electrolyte 10,310,48 Terminal 9,39,49,59 External power supply 6,36,44,54 Container 104,204 Bottom plate 105,205 Fixer 106,206 Pressure vessel 107,207 Electrolyte vessel 108, 208 Plug 109, 209 Reference electrode 110, 210 Thermocouple 111, 211 Electrolyzer holder 112, 212 Pressure vessel lid 113, 213 Heater 114, 214 Gas pipe 115, 215 Deuterium gas

Claims (3)

[Claims] 1. Energy is generated by using an energy generator of a type in which a voltage is applied to an anode and a cathode essentially consisting of a hydrogen storage metal or its alloy in heavy water containing an electrolyte to cause an energy generating reaction. In the method of causing the generation reaction, the following formula is obtained by supplying deuterium gas to the anode. A method of generating energy, which comprises causing a reaction of deuterium gas as shown in 1 to be converted into deuterium ions. _{2. A} deuterium D ₂ gas to an anode in an energy generator of the type in which a voltage is applied to the cathode consisting essentially of a hydrogen-storing metal or an alloy thereof in contact with heavy water containing an electrolyte and to the anode. An energy generating device, characterized in that it has means for introducing it. 3. An energy acquisition device in which energy extraction means is added to the energy generation device according to claim 2.